Photographic processes

ABSTRACT

Exposed photographic silver halide emulsions containing development inhibitor releasing coupler are processed in the presence of primary aromatic color developing agent and a competing coupler which produces substantially no permanent dye in the emulsion.

United States Patent Inventor Nicholas R. Groet Rochester, N.Y.

Appl. No. 764,599

Filed Oct. 2, 1968 Patented Oct. 26, 1971 Assignee Eastman Kodak CompanyRochester, N.Y.

PHOTOGRAPHIC PROCESSES 12 Claims, No Drawings U.S. Cl 96/55, 96/56.5,96/56.6 Int. Cl G03c 7/00 Field of Search 96/55, 22, 48, 66.3

Primary Examiner-Norman G. Torchin Assistant ExaminerAlfonso T. SuroPico Anorneys--W. H. J, Kline, .l. R. Frederick and O. H. WebsterABSTRACT: Exposed photographic silver halide emulsions containingdevelopment inhibitor releasing coupler are processed in the presence ofprimary aromatic color developing agent and a competing coupler whichproduces substantially no permanent dye in the emulsion.

PHOTOGRAPHIC PRQCESSES This invention relates to novel photographicprocesses, and more particularly to novel photographic processes whichresult in the good reproduction of both fine line and continuous toneimages.

Photographic processes are known, such as those utilizing commerciallyavailable microfilm, which produce the high contrast required forrecordingfine line copy. Such films have a relatively short latitude,and record continuous tone images poorly. It therefore appears highlydesirable to provide novel photographic processes which record fine linecopy satisfactorily and at the same time produce acceptable continuoustone images. Such processes should result in very high contrast forprinted material or small image areas (i.e., high microcontrast ormicrogamma) and low contrast for large or continuous tone image areas(i.e., low macrogamma or macrocontrast). The images provided by suchprocesses should preferably be composed predominantly of silver toprovide a permanent record. Images composed primarily of dye are notsuitable for certain purposes, such as when the images are to be storedfor an extended period of time.

One object of this invention is to provide novel photographic processes.

Another object of this invention is to provide novel photographicprocesses which yield high-contrast images of fine line copy.

A further object of this invention is to provide novel photographicprocesses which produce good continuous tone images.

Another object of this invention is to provide novel photographicprocesses which result in images which exhibit good edge effects.

Still another object of this invention is to provide photographicprocesses-which result in images that exhibit high microcontrast and lowmacrocontrast.

Still other objects of this invention will be apparent from thedisclosure herein and the appended claims.

In accordance with this invention, an improvement is provided in themethod of developing, with primary aromatic color developing agent, animagewise exposed photographic element comprising a support havingcoated thereon a photographic silver halide emulsion layer containing adevelopment inhibitor releasing coupler. The improvement comprisesconducting development in the presence of a competing coupler whichproduces substantially no permanent dye in the emulsion layer.

in preferred embodiments of the invention, the photographic silverhalide emulsion layer comprises fine silver halide grains, and thedevelopment is conducted in the presence ofa silver halide solvent.

in another embodiment of this invention, the novel processes describedabove are enhanced by conducting development in the presence of anauxiliary developer.

The processes of the invention employ a competing coupler which producesubstantially no permanent dye in the emulsion layer. The coupler may beone which, on reaction with oxidized color developing agent, forms nodye (a leuco dye) or forms a dye that is removed from the coating uponwashing in aqueous processing solution. The competing coupler utilizedis preferably one which forms a diffusible dye on reaction with oxidizedaromatic primary amino color developing agent. The dye formed isdiffusible and washes out of the layer. Competing couplers of this typeare described and referred to in Weller et al. U.S. Pat. No. 2,689,793,issued Sept. 21, 1954, and Salminen U.S. Pat. No. 2,742,832, issued Feb.17, 1955, the disclosures of which are incorporated herein by reference.

Competing couplers which form colorless reaction products with primaryaromatic amino color developing agents are described by Puschel, On theChemistry of White Couplers" Agfa-Gevaert A.G. Mitteilangen aus denForschingslaboratorien der Agfa-Gevaert A.G.. Spinger Verlay, 1954,pages 352-367; French Pat. No. 1,340,552 Sept. 9. i963); and BritishPat. No. 907,274 1962) l962)**which disclosures are incorporated hereinby-reference.

Particularly good results are achieved in the practice of this inventionwith the competing coupler 4-carboxy-2, 6- dihydroxypyridine (citrazinicacid or CZA) and 3,6-disulfo-8- amino-l-naphthol (ll-acid). Otherspecific useful couple compounds that can be employed are listed below:I

2-amino-5-naphthol-7-sulfonic acid--.l-acid l,8-dihydroxynaphthalenedisulfonic acid-chromotropic acid 1-naphthol-3,6,8-trisulfonic acidl-naphthol-Z-sulfonic acid p-(w-Benzoylacetamino) benzene-sulfonic acid2,4-di-nitrophenylacetic acid 1-amino-8 -naphthol-2 ,4disulfonic acidl-napthol-4,8-disulfonic acid l-p-sulpphenyl-3-methyl-5 -pyrazolonel-phenyl-3-meta-sulfobenzamido-S -pyrazolone l-naphthol-5-sulfonic acidThe competing coupler can be incorporated in the emulsion layer itselfif desired. However, it is preferred to employ the competing coupler inthe developer solution.

The term development inhibitor-releasing coupler" is used herein as aword of art to refer to those photographic couplers which, upon reactionwith oxidized primary aromatic amine color developing agent, form dyeand release a compound which inhibits development. The developmentinhibitorrcleasing couplers which are utilized in the-practice of thisinvention can embody any photographic coupler radical. Typical usefulphotographic coupler radicals include the 5- pyrazolone couplerradicals, the phenolic (including anaphthol) coupler radicals, and theopen-chain ketomethylene coupler radicals. As is well known in the art,5- pyrazolone coupler radicals are customarily utilized for theformation of magenta dyes; phenolic coupler radicals are generallyutilized for the formation of cyan color dyes; and, open-chainketomethylene coupler radicals are generally utilized in the formationof yellow dyes. The coupling position of such coupler radicals is alsowell known in the art. The 5- pyrazolone coupler radicals couple at thecarbon atom in the 4-position thereof; the phenolic coupler radicalscouple at the carbon atom in the 4-position (relative to the hydroxylgroup); and, the open-chain ketomethylene coupler radicals couple at thecarbon atom forming the methylene moiety (e.g.

wherein denotes the coupling position).

Development inhibitor-releasing (DIR) couplers which can be utilizedherein can be represented by the general formula:

wherein Cp represents a photographic coupler radical, preferably anopen-chain ketomethylene, S-pyrazolone or phenolic (includingalpha-naphtholic) coupler radicals, having said 2 substituted in thecoupling position of the coupler radical, Z representing an organicgroup which does not contain a chromophore, does not couple withoxidized primary aromatic amine colordeveloper to form dye, does notinhibit development while attached to Cp, but is released from Cp, onreaction with oxidized primary aromatic amine color developing agent,and either is or forms a compound which inhibits development.

An especially useful class of. open-chain ketomethylene coupler radicalsis described in Formula 1 below:

Formula I I R1-?Yl wherein R, and X, represent substituents of the typeused in open-chain DIR ketomethylene couplers. For example R, can

represent an alkyl group (which can be substituted and preferably hasfrom about six to 22 carbon atoms); an aryl group (preferably a phenylor naphthyl group); or, a heterocyclic group (preferably a carboncontaining heterocyclic radical which contains from five to six atoms inthe heterocyclic ring, which ring contains at least one hetero oxygen,sulfur or nitrogen atom); X, can represent a member selected from thegroup consisting of cyano and carbamyl (which can be substituted); and,Y represents a group which, when released from the coupler on reactionwith primary aromatic amine color developing agent, either is or forms acompound which inhibits development. Y, can represent:

2a monothio group, such as ortho-nitro or ortho-amino substitutedarylmonothio groups (such as, 2-nitrophenyl and Z-aminophenyl), a carboncontaining heterocyclic monothio group (generally having a five to sixmembered ring containing at least one heteronitrogen, oxygen or sulfuratom and preferably one to four heteronitrogen atoms) includingheterocyclic radicals, such as, tetrazolyls, triazinyls, triazolyls,oxazolyls, oxadiazolyls, diazolyls, thiazyls, thiadiazolyls,benzoxazolyls, benzothiazolyls, pyrimidyls, pyridinyl, quinolinyls,etc., and in which the aryl-,'heterocyclic-- moieties of the monothiogroup are either unsubstituted or substituted with various groups, suchas nitro, halogen (chlorine, bromine, iodine, fluorine), lower alkyl,lower alkylamido, lower alkoxy, lower alkylsulfonamido,achloroacetylthio, lower alkylcarbamyl amino, etc., typical monothiogroups representing the above include 2- aminophenyl, 2-nitrophenyl anda heterocyclic group (e.g. 2-benzothiazolylthio,1-phenyl-5-tetrazolylthio, l- (4-carbo-methoxyphenyl) S-tetrazolylthio,S-phenyll,3,4-oxadiazolyl-2thio, 2-phenyl-5- l ,3 ,4 )-ox- Vadiazolythio, 2-benzoxazolylthio, etc.);

2. a Z-aminoarylazoxy group (e.g. Z-aminophenylazoxy, 2-

amino-4-chlorphenylazoxy, etc.);

3. a 2-amidoarylazoxy group (e.g., Z-acetamidophenylazoxy,2-acetamido-4-methylphenylazoxy, 2-acetamido-4- chlorophenylazoxy,2-palmitamidophenylazoxy, 4- methoxy-2-palmitamidophenylazoxy,4-chloro-2-palmitamidophenylazoxy, etc.);

4. a 2-aryltriazolyl group (e.g., 2-benzotriazolyl, -chloro-2-benzotriazolyl, 5-hydroxy-2-benzotriazolyl, 4,7-dinitro-2-benzotriazolyl, 5-methyl-2-benzotriazolyl, 6-methoxy-2- benzotriazolyl,4-carboxyethyl-2-benzotriazolyl, 4-sulfoethyLZ-benzotriazolyl,Z-naphthotriazolyl,4-methyl-2- naphthotriazolyl,5-chloro-2-naphthotriazolyLS-hydroxy- Z-naphthotriazolyl, 5-nitro-2naphthotriazolyl 5-sulfoethyl-Z-naphthotriazolyl,4-amino-2-naphthotriazolyl, benzo[l,2-d:4,5-d']- bistriazolyl, etc.).The coupler forms a diffusible mercaptan when Y represents (1) above,and a diffusible aryltriazole when Y represents (2), (3) or (4) above,upon reaction with oxidized color developing agent.

The development inhibitor releasing couplers utilized in this inventioncan feature a S-pyrazolone coupler radical having the following generalformula:

Formula II wherein R and R, represent substituents of the type used in5- pyrazolone couplers, for example, R,, can represent a value given forR',; R can represent a member selected from the group consisting of analkyl group, a carbamyl group (which can be substituted), an aminogroup'(which can be substituted with various groups such as one or twoalkyl or aryl groups), an amide group, e.g., a benzamido group (whichcan be substituted), or an alkylamido group (which can be substituted),and, Y represents a value given above for Formula III OH wherein R R Rand R can represent a substituent of the type used in phenolic couplers,for example, R and R each can represent a value given for R and inaddition can represent a member selected from the group consisting ofhydrogen, amino, carbonamido, sulfonamido, sulfamyl, carbamyl, halogenand alkoxy; R and R when taken together, can represent the carbon atomsnecessary to complete a benzo group, which benzo group can besubstituted with any of the groups given for R and R and, when takenseparately, R and R can each independently represent a value given for Rand R and Y represents a value given above for Y,.

Representative DIR couplers include the following:

1. a-Benzoyl-a-(2-nitrophenylthio)-4-[N-(y-phenylpropyU-N-(p-tolyl)-sulfamyl]acetanilide a-Benzoyl-a-( 2-benzothiazolylthio)-4-[ N-( y-phenylpropyl)-N-(p-tolyl)sulfamyllacetanilide 3, a-{3-[a-(2,4-di-tert-amylphenoxy)butyramidol-benzoyl}-aZ-meihoxyacetanilide 4.a-l3-[y-(2,4-ditert-amylphenoxy)butyramido1-benzoyl }-a-2-be'nzoxazolylthio) 2-methoxyacetanilide 5. a-Benzoyl-a-M l-(3-phenyl)-5 -tetrazolythio]stearam ido acetanilide 6.a-{3-[a-(2,4-di-tert-arnylphenoxy)butyrarnido]benzoyl}-a-(Z-aminoplmnylazoxy)-2-methoxyacetanilide 7. a-{3-['y-(24-di-tert-amylphenoxy)butyramido]-benzoyl-a- Q-amino-jgnethylphenylazoxy)-2-rnethoxy-acetanilide s. a-(5-Chloro-2beiizotriazolylyapivzfiyl-fla-(2,4-di-tertamylphenoxy)propylamido]-2-chloroacetanilide9. a-(4,7-Dinitro-2-benzotriazolyl)-a-pivalyl-3,6-dichloro-4-(N-methyl-N-octadecylsulfamyl)acetoacetanilide 10. a-(6-Chloro-5-methoxy-2-benzotriazoyl )-a-pivaly2- chloro-5-[a-(3-pentadecyl-4sulfophenoxy)-butyremido ]acetanilide, sodium salt 1 l.l-Phenyl-3-octadecylamino-4-[2-phenyl-5( l,3,4)-oxadiazolylthio]-5-pyrazolone l2.l-{4-[y-(2,4di-tert-amylphenoxy)butyramidol-phenyl 3-ethoxy-4-(l-phenyl-5-tetrazolylthio-5-pyrazolone l3.1-{4-[a-(Bpentadecylphenoxy)butyramidolphenyll -3- ethoxy-4-(l-phenyl-5-tetrazolylthio )-5-pyrazolone l4.l-(2,4,6-trichlorophenyl)-3-{4-[a-(2,4-di-tertamylphenoxy)butyramidolanilino-4-(l-phenyl-5- tetrazolylthio)- 5-pyrazolone l5.l-Phenyl-3-octadecylamino-4-( l-phenyl-5-tetrazolylthio 5-pyrazolone l6.l[4-( 4-tert-butylphenoxy)phenyl]-3-phenyl-4-( l-phenyl-S-tetrazolylthio) -5-pyrazolone 17.l-[4-(4-tert-butylphenoxy)phenyl]-3-[ a-(4-tert-butylphenoxy)propionamido]-4-( S-phenyll ,3 ,4-oxadiazolyl -2-thio)-5-pyrazolone l8. 1-[4-(4-tert-butylphenoxy)phenyl]-3-[a-(4-tert-butylphenoxy)propionamido]-4-(2-nitrophenylthio)-5-pyrazolone l9.l-[4-(4-tert-butylphenoxy)phenyll-3-la-(4'tert-butylphenoxy)propionamido]-4-[l-(4-methoxyphenyl)- 5- tetrazolylthio]-5-pyrazolone 20. l-[4-(4-tert-butylphenoxy)phenyl1-3-[a4-tert-butylphenoxy)propionamido1-4-(.2*benzothiazolylthio)-5-pyrazolone 21. l-[4-tert-butylphenoxy)phenyl]-3-[a-(4-tert-butylphenoxy)propionamido]-4-(2-nitrophenylthio5- pyrazolonel-[4-(4-tert-butylphenoxy)phenyl]-3-[a-(tert-bu- 22.tylphenoxy)propionamido]-4-(2-benzoxazolylthio pyrazolone 23.1-(2,4-dichloro-6-methoxyphenyl)-3-[a-(3-pentadecylphenoxy)acetamido]-4-(1-phenyl5-tetrazolylthio)-5- pyrazolone 24. l-Phenyl-3-octadecyl-4-(l-phenyI-5-tetrazolylthio)-5- pyrazolone 25l-Phenyl-3-[-(2,4-di-tert-amylphenoxy)acetamido]-4-(lphenyl-S-tetrazolylthio)-5-pyrazolone 26.l-Phenyl-3-['y-(2,4-di-tertamylphenoxy)butyramido1-4-l-phenyI-5-tetrazolylthio)-5-pyrazolone 27.l-Phenyl-3-(3,5-didodecyloxybenzamido)-4-(2-nitrophenylthio)-5-pyrazolone 28.l-Phenyl-3-[a-(2,4-di-tert-amylphenoxy)acetamido]-4-(2-aminophenylazoxy)-5pyrazolone 29.4-Benzotriazolyl-3-pentadecyl-l-phenyl-S-pyrazolone 30.4-Benzotriazolyl-l-(2,4,6-trichlorophenyl)-3-[3-{a-(2,4-di-t-amylphenoxy)acetamido }benzamido]-5-pyrazolone 31.4-(5-Methoxy-Z-benzotrizizolyl)-3-pentadecyll -phenyl-5- pyrazolone 32.4-(4Carboxy,2-benzotriazolyl)-l-(2,4,6-trichlorophenyl-3-pentadecyI-5-pyrazolone 3 3 l-I-Iydroxy-4-( 2-nit'rophenylthio)-N-[8-(2 ,4-di-tertamylphenoxy)butylI-Z-naphthamide 34.l-Hydroxy-4-(2-benzothiazolylthio)-N-[8-(2,4-di-tertamylphenoxy)butyl]-2-naphthamide35. l-Hydroxy-4-(l-phenyI-5-tetrazolylthio)-N-[8-(2,4-ditert-amylphenoxy)butyl]-2-naphthamide36. l-Hydroxy-4-(2-benzothiazolylthio)-N-octadecyl-3, 5"dicarbOXy-Z-naphthanilide 37. I -Hydroxy-4-(1-phenyl-5-tetrazolylthio)-2-tetradecyloxy- Z-naphthanilide 38.l-Hydroxy-4-[ l-(4-methoxyphenyl)-5-tetrazolylthiol-N- [8-(2,4-di-tert-amylphenoxy)butyl-2-naphthamide 39.l-I-Iydroxy-4-(5-phenyl-l,3,4-oxadiazolyl-2-thio) N-IS-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide 40.5-Methoxy-2-[a-(3-n-petadecylphenoxy)butyramido1-4-l'phenyl-5-tetrazolylthio)phenol 41.l-I-lydroxy-4-(2-amino-4-methylphenylazoxy-N-[8-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide 42.4-(2-Benzotriazolyl)-2-[8-(2,4-diamylphenoxybutyl)]-1-hydroxynaphthamide 43. l-I-l ydroxy-4-( 6-nitro-2-benzotriazolyl )-N-[8-( 2 ,4-di-tamylphenoxy)butyl]-2naphthamide 44.5-Methoxy-2-[a-(3-pentadecylphenoxy)butyramidol-4-(S-chloro-2-benzotriazolyl)phenol 45.5-Methoxy-2-[a-(3-pentadecylphenoxy)butyramido1-4-(6-chloro-5-methoxy-Z-benzotriazolyl)phenol Couplers 1 through 5, 11through 27, 33 through 40 are described in Barr U.S. Pat. No. 3,227,554.Couplers 6, 7, 28 and 41 are prepared by methods similar to thosedisclosed in U.S. Pat. No. 3,148,062. Couplers 8 through 10, 29 through32 and 42 through 45 are described by Sawdey U.S. Pat. application Ser.No. 674,090, filed Oct. 10, I967. The couplers referred to in theimmediate paragraph are the DIR couplers listed above.

The most useful DIR couplers are those which have a monothio group inthe coupling position (e.g., Formula I, II and III above in which Y,, Yand Y represent a monothio group). Preferred DlR couplers have FormulaI, II or III above wherein Y Y, and Y each represents a heterocyclicmonothio radical in which the heterocyclic ring has from five to sixatoms and at least one hetero atom selected from oxygen, sulfur andnitrogen, such as a hetero ring, containing from one to four heteronitrogen atoms, e.g., a 5-tetrazolylthio group.

Any suitable light sensitive silver halide can be employed in theprocess of this invention. Suitable silver halides include silverchloride, silver bromide, silver chlorobromide, silver chloroiodjde,silver bromoiodide, and silver chlorobromoiodide. The silver halidegrains canbe of any grain size, although particularly good results areobtained in the practice of this invention when fine grain silver halideis utilized. As used herein and in the appended claims, fine" silverhalide grains refers to silver halide grains having an average grainsize of up to about 0.5 micron, such as from about 0.1 to 0.5 micron.The silver halide emulsions can be either negative or direct positiveemulsions. Especially good results are obtained with negative typesilver halide emulsions.

The photographic coating used in the invention is developed withphotographic alkaline color developing solutions containing aromaticprimary amino color developing agents. Such developing agents are wellknown in the art and typically are p-phenylenediamines. Suitable colordeveloping agents include 3-acetamido-4-amino-N,N-diethylaniline,pamino-N-ethyl-N-B-hydroxyethylaniline sulfate,paminoethyl-BN,N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, N-ethyl-Bmethanesulfoamidoethyl- 3-methyl-4-aminoaniline, 4-amino-N-ethyI-3-methyl-N-Bsulfoethyl)anilineand the like. Reference is also made to Bent et al., JACS 73, 3100-3125(1951) for additional typical suitable color developing agents.

As indicated heretofore, fine grain silver halide is utilized inpreferred embodiments of the invention. When fine grain silver halideemulsions are utilized in the processes of memvention, development ispreferably conducted in the presence of silver halide solvent. Anysuitable silver halide solvent can be utilized. Typical silver halidesolvents useful herein are alkali thiosulfates, thiocyanates andcyanides; thiourea; thiocyanamine; and, ammonium hydroxide. Preferredresults are obtained with sodium thiosulfate and sodium thiocyanate.

In some instances, it is desirable to achieve satisfactory developmentat relatively high temperatures, such as about 40 C. up to 60 C., inrelatively short periods, such as l, 2 or 3 minutes. It has been foundas an additional feature of the present invention that such hightemperatures and short development times can be achieved by utilizing anauxiliary (i.e., noncolor) developing agent. The auxiliary developer canbe one typically employed as a black-and-white developing agent, such asa 3-pyrazolidone or an aminophenol. Especially useful results areobtained with such developers as l-phenyl- 4,4-dimethyI-B-pyrazolidone;l-phenyl-3-pyrazolidonc or methyl-p-aminophenol.

The optimum concentrations of the various materials utilized in theprocesses of this invention are interrelated and vary with the type ofparticular compound used. For example, the concentration of DIR couplerneeded to provide best results will depend upon the reactivity of theDIR coupler itself, and the effectiveness of development inhibitionproduced by the moiety split off from the DIR coupler upon reaction withoxidized color developing agent. The concentration of the DIR couplerutilized will further be dependent upon the particular competingcoupler, auxiliary developer and silver halide solvent. Generallyspeaking, good results can be obtained by employing concentrations offrom about 0.1 to 20 percent, and preferably from about 1 to 15 percentof the DIR coupler based on the weight of the silver in the coating.Competing coupler is advantageously employed in the processing solutionat concentrations of from about 0.05 to 20 g., and preferably from 1 to15 g. per liter. Generally good results are obtained using silver halidesolvent in a concentration of from 0.05 to 30 g., and preferably from0.5 to 20 g. per liter of developer solution. Auxiliary developer can beemployed within the general range of about 50 to 500 and preferably fromto 300 mg. per liter of developer solution. In certain instances, goodresults can be obtained operating outside of any or all of these ranges.

The emulsions employed in the practice of this invention can be coatedon any suitable support, such as paper or polyethylene coated paper, orfilm base such as cellulose triacetate or poly(ethylene terephthalate).The emulsions can contain the chemical sensitizers, speed increasingcompounds, plasticizers, hardeners and coating aids, and the silverhalide may be dispersed in any of the binders, that are described andreferred to in Graham et al. U.S. Pat. No. 3,046,129 issued July 24,1962. The couplers used in the invention can be incorporated in theemulsion in any suitable manner, such as by the processes described inU.S. Pat. Nos. 2,322,027 or 2,801,171.

The following examples are included for a further understanding of theinvention.

EXAMPLE I A photographic element is prepared by coating a celluloseacetate support with a gelatin silver bromoiodide emulsion, the grainsof which are between about 0.1 and about 0.5 micron in diameter, at acoverage of 190 mg. per square foot silver, 300 mg. per square footgelatin. The coating also contains 9 mg. per square foot of the DIRcoupler l-hydroxy-4-(lphenyl-S-tetrazolylthio)-2-(2-n-tetradecyloxy)naphthanilide, dissolvedin suitable coupler solvent such as tri-o-cresyl phosphate. Samples ofthe film are exposed through a step tablet and to X-ray lines 10, 100and 1000 microns in width. After exposure, thefilm is developed for 13minutes at about 20 C. in the following developer composition:

Water 950 ml. Benzyl alcohol 3.8 ml. Sodium polyphosphate 2.0 g. Sodiumsulfite (desicc.) 2.0 g. 10% NaOH Soln. 5.5 ml.

Color develo er 5.0 g. KBr 1.0 g. Nn,CO,(monohydr.) 50.0 g.' NaSCN 2.0g. 3,6-disulfo-8-aminoJ- naphthol 2.0 g.

Water to 1 liter p1 l=10.75

4-Amino-3 methyl-N-ethyl-N-fl-(methanesulfonamido)ethyl- 40 anilinesesquisulfate hydrate The element is then washed, fixed, washed againand dried. Microdensitometer traces of the three images are made and themaximum density at the edge and the center of the three lines are read(at 1.0 above gross fog) and the relative densities are shown in table 1below. It will be noted that in this example, as in the followingexamples, the center and the edge of he IO-micron line image haveessentially the same densities.

TABLE 1 Image Width D max 1000;]. 100 to,

. Edge ol'image 1.1 1.2 1.3 Center of image 0.7 0.9 1.3

EXAMPLE 2 The procedure of example 1 is repeated except that the DlRcoupler is omitted from the emulsion, and the silver halide solvent,sodium thiocyanate, is omitted from the processing solution. The resultsare shown in table 2:

TABLE 2 image Width D max. 1000 4. 10

Edge of image 0.6 0.6 0.5 Center of image 0.6 0.6 0.5

The above results show that this element is entirely unsuited to therecording of fine line images. This film actually has lower microgammathan macrogamma (showing inability to record continuous tone imagessatisfactorily). There are substantially no edge effects. The contrastis 4.2.

EXAMPLE 3 The procedure of example 1 is repeated except that the DlRcoupler is omitted from the emulsion coating. Processing is conducted inthe presence of silver halide solvent and compet- The above able showsthat the silver halide solvent in the developing solution in the absenceof DlR coupler, afford no practical edge effects. The macrocontrast issomewhat higher than the microcontrast. The contrast is 3.5.

EXAMPLE 4 The procedure of example 1 is repeated except that processingis conducted in the absence of silver halide solvent and competingcoupler. Exposure and processing are exactly as described in example 1.The results are shown in table 4.

TABLE 4 Image Width D max. 1000p. 100;) I011 Edge of image 0.2 0.3 0.4Center of image 0.2 0.3 0.4

The above results show that omission of competing coupler and silverhalide solvent in developing solution resulted in only no practical edgeeffects with extremely low image example being obtained. The contrast isundesirably low at 0.20.

EXAMPLE 5 The procedure of example 1 is repeated except that the silverhalide solvent is omitted during processing. Exposure, processing andtesting are exactly-as described in example 1.

5 The results are set out in table 5 below.

TABLE Image Width D max. 1000 100 image Width D iu 5 Edge of image 0.90.9 0.0 Center of image 0.9 0.9 0.8

Edge ofimage 1.0 l.l 1.0 Center of image 0.7 0.8 [.0

The above results show that the presence of DIR coupler in the emulsiontogether with competing coupler in the developing solution results inexcellent edge effects, and higher microgamma than macrogamma. Thecontrast of the film is 0.65. Edge effects are further enhanced by thepresence of silver halide solvent, as shown in example 1 above.

EXAMPLE 6 The procedure of example 1 is repeated except that theemulsion layer contains 130 mg. per square foot of the yellow dyeforming coupler, a-pivalyl-a-(4-carboxyphenoxy)-2- chloro-S-['y-(2,4-di-t-amylphenoxy)butyramidolacetanilide dissolved in 65 mg.tricresyl phosphate. The element obtained in accordance with thisexample as excessively high fog. When the example is repeated using theless reactive yellow dye forming coupler,a-pivalyl-Z-chloro-S-[y-(2,4-di-tamylphenoxy)butyramidol-acetanilide,the image contrast is far too low to be useful in recording fine lineimages.

EXAMPLE 7 A photographic element is prepared similar to that in exampie1 except that it contains on a cellulose acetate support a silverchlorobromide emulsion coated at 190 mg. silver per square foot and 154mg. of gelatin per square foot. Upon exposure as described in example 1,processing in conventional black-and white developer and testing as inexample 1, it is found that while the film has high contrast, itslatitude is poor resulting in unsatisfactory continuous tone images. Thedensity of the microimages at 10 and 100 micron widths are approximatelythe same, or somewhat lower, than that of the macroimage at 1000microns.

Examples 8 and 9 illustrate the improvement in reducing development timewith a black-and-white developer being incorporated in the processingsolution.

EXAMPLE 8 The procedure described in example i is repeated except thatthe temperature of the developing solution is raised from C. to 38 C. Byraising the temperature of the developing solution, the developing timeis reduced from 13 to 3 minutes. An undesirably high fog level isobtained.

EXAMPLE 9 The procedure described in example 8 is repeated except thatthe developing solution contains in addition 250 mg. oflphenyl-4,4-dimethyl-3-pyrazolidone per liter of solution. Thedevelopment time is hereby further reduced from 3 to 1% minutes and theincrease in fog obtained by the procedure according to example 8 is notobserved.

EXAMPLE 10 A sample ofa high-definition film comprising a single-layergelatin silver chlorobromide emulsion containing 137 mg. of silver persquare foot on a poly(ethylene terephthalate film base is exposed as inexample i and conventionally black-andwhite developed, fixed, washed anddried. The gamma of the film is 2.6, and the microdensitometer tracesgive the results shown in table 6.

TABLE 6 The results in table 6 show that the macrogamma is undesirablyhigher than the microgamma.

EXAMPLE 1 l TABLE 7 Image Width D max. I000 100 [0 Edge of image 1.4 1.51.7 Center of image 0.9 l .0 L7

The above table 7 shows the excellent ratio of microgamma to macrogamma,as well as the good edge effects obtained in the v practice of thisinvention. The contrast of the film is 3.2.

EXAMPLE 12 The procedure of example H is repeated except that thecoating does not contain DIR coupler. The results are shown in Table 8.

TABLE 8 image Width D max. 1000 [0 Edge of image 1.3 l 1 Center of image[.3

The above results demonstrate the undesirably high macrogamma (whichmeans shortened exposure latitude) with moderate improvement in edgeeffects. The contrast is 4.5.

The invention has been described in detail with particular reference topreferred embodiments thereof, but, it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention described hereinabove and in the appended claims.

1. A method for obtaining both high microcontrast and a lowmacrocontrast in developed photographic silver images, comprisingdeveloping a photographic element containing an exposed fine grainsilver halide photographic emulsion and development inhibitor-releasingcoupler with a color develop ing agent in the presence of a competingcoupler which reacts with said color developing agent to produce leucoor a soluble wash removable dye removing said soluble dye whereproduced, and obtaining an essentially colorless black and white image.

2. The method of claim 1 wherein said development is conducted in thepresence of an auxiliary black-and-white developing agent.

3. The method of claim 1 wherein said development is conducted in thepresence of a silver halide solvent.

4. The method of claim 1 wherein said development inhibitor releasingcoupler has a monothio group in its coupling position which, uponreaction with oxidized primary aromatic amino color developing agent,forms a diffusible mercaptan that inhibits development; and, saidcompeting coupler forms diffusible dye on reaction with said oxidizedaromatic primary amino color developing agent.

5. The method of claim 4 wherein said development inhibitor releasingcoupler has one of the following structural formulas:

Formula I (l) H Ri-JJ-+ i Formula II N=CRa RsN /H ii Y Formula III 0HRn- R10 wherein R, and R each represents a member selected from thegroup consisting of alkyl, aryl, and a heterocyclic group containing atleast one hetero atom selected from oxygen, sulfur and nitrogen; Xrepresents a member selected from the group consisting of cyano andcarbamyl; R represents a member selected from the group consisting ofalkyl, carbamyl, amino, amido, benzamido, and alkamido; R and R eachrepresents a member selected from the group consisting of hydrogen,alkyl, aryl, a heterocyclic group containing at least one hetero atomselected from oxygen, sulfur and nitrogen, amino, carbonamidosulfonamido, sulfamyl, carbamyl, halogen and alkoxy; R and R when takentogether, represents the atoms required to complete a benzo group, andwhen taken separately, each represents a value selected from those givenfor R and R and, said Y Y and Y each represents a monothio groupselected from an orthoaminosubstituted arylmonothio group; anorthonitro-substituted arylmonothio group; and, a heterocyclic radicalcontaining at least one hetero atom selected from oxygen, sulfur andnitrogen, to complete said coupler.

6. The method of claim 5 wherein said development inhibitor releasingcoupler is employed at a concentration of from about 0.1 to about 20percent by weight of the silver in said coating; development isconducted with an aqueous processing solution containing the developingagent; said competing coupler is employed in the processing solution ata concentration of from about 0.05 to about 20 g. per liter; and, saidsilver halide solvent is employed in the processing solution at aconcentration of from about 0.05 to 30 g. per liter.

7. The method as defined in claim 6 wherein said processing solutioncontains about 50 to mg. per liter of auxiliary black-and-whitedeveloping agent.

8. The method of claim 1 wherein the silver halide emulsion containsl-hydroxy-4-( l-phenyl-S-tetrazolythio )2-( 2-ntetradecyloxy)naphthanilide dissolved in coupler solvent as adevelopment inhibitor releasing coupler.

9. The method of claim 8 wherein the developer solution contains anaromatic primary amino color developing agent, about 2 grams of3,6-disulfo-8-amino-l-napthol per liter of developer solution, and about2 grams sodium thiocyanate per liter of developer solution.

10. The process of claim 8 wherein said development is conducted in thepresence of about 250 mg. per liter of developer solution of l-phenyll,4-dimethyl-3-pyrazolidone.

l l. A photographic process comprising:

A. contacting a photographic element having an exposed fine grain silverhalide photographic emulsion with an average diameter of from 0.1 to 0.5micron and containing a development inhibitor-releasing photographiccoupler selected from the group consisting of:

a. a S-pyrazolone b. an open chain ketomethylene, and c. a phenolicphotographic coupler, said inhibitor-releasing coupler having a monothiogroup in coupling position, with a photographic developer solutioncontaining 1. an aromatic primary amino color developing agent;

and 2. about 0.05 to 30 grams ofa silver halide solvent per liter ofdeveloper solution, the development step being effected in the presenceof a competing coupler which reacts with oxidized color developing agentto produce a leuco or a soluble wash remova ble dye, and

B. washing out the soluble dye where produced to obtain an essentiallycolorless black and white image.

12. The photographic process defined in claim 11 wherein said developersolution contains an auxiliary developer selected from the groupconsisting of a 3-pyrazolidone developing agent and an aminophenoldeveloping agent.

3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3 5 A9? dFebruary 21 1972 Patent No. Date Inventor) Nicholas H Groet It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, line 73, after "Pat. No. l,3 lO,522" and before "Sept." inserta parenthesis line 7 4, after "907,72U" and before "1962" insert aparenthesis and after "1962? (first occurrence, delete "l962)**.

Column 3, line 13, replace "2" with l-- line 3, replace "2-phenyl-5-l,3,l)-ox-" with -p y 5( ,3, lines 36 and 37, replace both lines with a 2-aminoarylazoxy group (e.g. 2-amino-M- methylphenylazoxy,2-aminopheny1azoxy, 2- amino-H-chlorphenylazoxy, etc.)

Column 4 lines 30-31 replace both lines with 3 6-; {3-1,};

(2,M-di-tert-amylphenoxy)butyramidg/ benzoyl} L2nitrophenylthio-2-methoxyacetanilide;

line 32, replace ditert-" with --ditert line 33, after"(2-benzoxazolylthio)" insert a hyphen line 3 4 replace entire line with5 o Benzoyl-0 T(3 phenyl)5-tetrazolylthi /stearamido line 10, replace;pivalyl-" with L-pivalylalso after "-5" insert a hyphen lin L15 replace"pivaly" with pivalylline 48, after "2-phenyl-5" insert a hyphen line 50after T 2 l insert a hyphen line 51, after "S-tetrazolylthio" insert aparenthesis line 55, after "anilinojf delete the first hyphen;

Pa e l of 2 a es L 8 P E J UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. a Dated February 21 7 Nicholas H. Groet PAGE 2Inventor(s) It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 57, after "5-tetrazolylthio" insert a parenthesis and ahyphen line 70 after "A? insert a hyphen followed by a parenthesis line7, after *2-nitorphenylthio" insert a parenthesis and a hyphen line 75,replace "pyrazOlone" with pyrazolone-.

Column 5, line 2, after "benzoxazolythio" insert a parenthesis and ahyphen line 5, after "-U-(l-phenyl" insert a hyphen line 9, after "3-K"insert line 22, replace entire line with -32. l-(U-Carboxy-2-benzotriazolyl)-l-(2, l,6-trichlorophenyl).

Column 6 line 15 after "aminoethyl-fi insert -hydroxyaniline line 16after "N-ethyl-fl insert a hyphen line 17, after "-N-fl insert a hyphenColumn 7, line 51, replace "he" with the--.

Signed and sealed this 13th day of June 1972.

(SEAL) Attest:

EDWARD M. FLETCHER,JR.

Attesting Officer ROBERT GOTTSCHALK Commissionerof Patents

2. The method of claim 1 wherein said development is conducted in thepresence of an auxiliary black-and-white developing agent.
 2. about 0.05to 30 grams of a silver halide solvent per liter of developer solution,the development step being effected in the presence of a competingcoupler which reacts with oxidized color developing agent to produce aleuco or a soluble wash removable dye, and B. washing out the solubledye where produced to obtain an essentially colorless black and whiteimage.
 3. The method of claim 1 wherein said development is conducted inthe presence of a silver halide solvent.
 4. The method of claim 1wherein said development inhibitor releasing coupler has a monothiogroup in its coupling position which, upon reaction with oxidizedprimary aromatic amino color developing agent, forms a diffusiblemercaptan that inhibits development; and, said competing coupler formsdiffusible dye on reaction with said oxidized aromatic primary aminocolor developing agent.
 5. The method of claim 4 wherein saiddevelopment inhibitor releasing coupler has one of the followingstructural formulas:
 6. The method of claim 5 wherein said developmentinhibitor releasing coupler is employed at a concentration of from about0.1 to about 20 percent by weight of the silver in said coating;development is conducted with an aqueous processing solution containingthe developing agent; said competing coupler is employed in theprocessing solution at a concentration of from about 0.05 to about 20 g.per liter; and, said silver halide solvent is employed in the processingsolution at a concentration of from about 0.05 to 30 g. per liter. 7.The method as defined in claim 6 wherein said processing solutioncontains about 50 to 100 mg. per liter of auxiliary black-and-whitedeveloping agent.
 8. The method of claim 1 wherein the silver halideemulsion contains1-hydroxy-4-(1-phenyl-5-tetrazolythio)2-(2''-n-tetradecyloxy)naphthanilidedissolved in coupler solvent as a development inhibitor releasingcoupler.
 9. The method of claim 8 wherein the developer solutioncontains an aromatic primary amino color developing agent, about 2 gramsof 3,6-disulfo-8-amino-1-napthol per liter of developer solution, andabout 2 grams sodium thiocyanate per liter of developer solution. 10.The process of claim 8 wherein said development is conducted in thepresence of about 250 mg. per liter of developer solution of1-phenyl-1,4-dimethyl-3-pyrazolidone.
 11. A photographic processcomprising: A. contacting a photographic element having an exposed finegrain silver halide photographic emulsion with an average diameter offrom 0.1 to 0.5 micron and containing a development inhibitor-releasingphotographic coupler selected from the group consisting of: a. a5-pyrazolone b. an open chain ketomethylene, and c. a phenolicphotographic coupler, said inhibitor-releasing coupler having a monothiogroup in coupling position, with a photographic developer solutioncontaining
 12. The photographic process defined in claim 11 wherein saiddeveloper solution contains an auxiliary developer selected from thegroup consisting of a 3-pyrazolidone developing agent and an aminophenoldeveloping agent.